Isomerization process



Feb. l5, 1949. H. J. HEPP I ISOMERIZATION PROCESS Y 2 Sheets-Sheet l F i1ed Aug. 7, 1944 ...Sbs

Feb. 15, 1949.

H. .,1. HEPPY ISOMERIZATION PROCESS 2 sheets-sheet Filed Aug. 7, 1944 SHOlVNOLLDVH NWO-|03 BdOtLLOBZV HOLDVBH .Lsl

INVENTOR H. J. HEPP ATTORNEYS www III

IIII...

Patented Feb. 15, 1949 autres oFFlci:

ISOMERIZATION PROCESS Harold J. Hepp, Bartlesville, Okla., assignor to hillipsv Petroleum Company, a corporation of Delaware Application August fz, i944, serial No. 548,379

'7 Claims.

This invention relates to the catalytic conversion oi normal hexane to isohexanes of high antiknock rating and more specifically diisopropyl and neohexane. More particularly, it relates to such a process wherein hydrogen fluoride containing 1 to 10 weight per cent of boron trifluoride based on the weight of hydrogen fluoride is used as the catalyst and wherein modifiers, namely hydrogen, .cycloparains -or aromatics are employed to minimize the formation. of homologs.

For background, attention is directed to the copending applications of F. E. Frey, Serial No. 460,867, led Oct. 5, 1942, directed to isomerization and reconstruction of C4 to C6` paraiiins with a catalyst consisting of hydrogen fluoride and from 1 to 10% by weight of boron triuoride based on theweight of hydrogen fluoride, and Serial No. 511,444, filed Nov. 23, 1943, directed to the use of water in a proportion not exceeding the molecular trifluoride in the isomerization or reconstruction of low-boiling normal parafns with a catalyst consisting of hydrogen fluoride and from 1 to 10% by weight of BFS based on the hydrogen fluoride,

and to the application of John L.l Richmond,

Serial No. 509,611, led November 9, 1943, and directed to the use of cycloparaiiins in amount up to 25% by weight of the hydrocarbon charge in such processes which are now known as Isoversion The principal object of the present invention is to provide an improved process for isomerizingl normal hexane to isohexanes of high antiknockrating in good yield. Another `Objectis to provide an economical process of the foregoing type which yields diisopropyl andalso neohexane usually in smaller amounts than the diisopropyl. Another object is to provide a two stage isomerization process of the foregoing type. is to provide such a two stage process wherein common fractionating means are used for fracy tionating the efuents from both stages and for preparing the feed and recycle stream to the second stage. Numerous other objects will hereinaiter appear.

equivalent of the boron vio Another object .(Cl. i560-683.5)

In the accompanying drawings, Figure 1 D01'- trays diagrammatically a preferred arrangement of equipment for use in carrying out the present invention. Figure 2 shows a modified arrangement of equipment which may be employed at some sacrifice of flexibility and yield.

The present invention comprises isomerizingnormal hexane in a first step or stage to form methyl pentanes as the principal product. The conditions of time,l temperature and catalyst composition usedin this step are relatively sever and relatively small amounts of modifiers selected from the group consisting of hydrogen, cycloparafns and aromatics are employed since normal hexane `is of high stability. The methyl pentanes thus formed being less stable than normal hexane are treated in-a second catalytic step or stage under relatively milderrconditions of time,l temperature or catalyst composition and larger amounts of restrainer or modier are used than were employed in the first step. By this means the relatively unstable diisopropyl is conserved. l

The catalyst used in each stage is hydrogen iluoride containing from 1 to 10 weight percent of boron trifluoride based on the weight of hydrogen uoride. As the modifier or restrainer I may use elemental hydrogen, cycloparafiins or aromatics or combinations of two or more thereof. As the cycloparaflin, I prefer to use methyl cyclopentane but I may employ other cycloparafns having from` 5 to '7. carbon atoms. in

the ring and alkyl derivatives thereof. As theA aromatic hydrocarbon employed as inhibitor, Ivv

prefer to use benzene and its homologs such as tolueneand xylene.

The process will now ence to Figure 1 of the drawing. The fresh normal hexane, modifier and a small amount of water passes via line I to the first reactor 2. Fresh catalyst enters via line 3. Recycled nor-` mal hexane enters via line 4. The effluent passes to settler =5 where itvseparates into an acid-rich, and a hydrocarbon-richphase. The acid phase is in part returned to reactor 2 via-line 6 and l"be described with refer-v in part passed via line l to a catalyst regenerator. The hydrocarbon phase passes via line 3 to azeotrope column il, the overhead from which, containing hydrogen fluoride, boron triuoride and some hydrocarbon is recycled to the reaction via line l. The kettle product from column Si passes via line ll to the fractionation system l2 which separates it into (l) a fraction of pentanes and lighter leaving via line i3, (2) a fraction of neoheXane and diisopropyl leaving via line l, (3) a fraction of methyl pentanes which is passed via line l to the second reactor I6, (4) a fraction of normal hexane which is recycled to the rst reactor Via line 4 and (5) a fraction of heptanes and heavier leaving via line l1.

The stream of methyl pentanes in line l5 is fed into the second reactor I6, appropriate amounts, of modifier and water being admixed therewith. Fresh catalyst is fed to reactor I6 via line I8. The effluent from reactor i6 passes to settler I9 where it is separated into a hydrocarbon phase which is fed via line to azeotrope column 2i and an acid phase which is .inV part returned to reactor i6 viaV line` 22and.i'n part withdrawn via line 23 for regeneration or disposal in any other manner.

In azeotrope column 2l the hydrocarbonphase is separated into an overhead of HF, BFH, and

some hydrocarbon which is recycled via line 24 and a kettle product which is fed via line .25 into'fractionating system i2.

A considerable simplification of the arrangement ofFigure l where hydrogen is shown as the modifier'is portrayed in Figure 2 which involves some sacrice of flexibility over the arrangement `of Figure 1. In Figure 2, the normal hexane in admixture with hydrogen is charged to thefrst reactor 3l via line 3l). Relatively high temperature and lower hydrogenA pressure are maintained vin reactor' 3l to effect maximum conversion of normal hexane to isohexanes. The eiiiuents are-cooled and after admixture with more hydrogen are passed via line 32 directly intoV the, second reactor, 33. TheY total vproducts are reacted in the second reactor usuallyI at somewhat :lower temperature. and relatively high hydrogen pressure. The effluents from reactor 33 pass to acid settler 34. The acid phase is in part recycled to reactor 3| and in part withdrawn. The hydrocarbon phase passes via line 35 to azeotrope column 3S. The overhead from azeotrone column 35 is condensed and separated into twophases. The upper or hydrocarbon layer which is composed of hexanes and lighter hydrocarbons and minor proportions. of hydrogen iluorde and boron triiluoride is in part employed as redux for column 3@ and the balance is withdrawn. via line 3'! whence it is in part recycled viav line 38 and Yin part withdrawn kto recovery vialine 39. The lower or acidlayer whichy is composed of .hydrogen fluoride. boron. triuoride. and small proportions of dissolved.. hydrocarbonsis passed via line. intoadmixture with the acid phase withdrawn from settler 34.

The kettle product from azeotrope column 36 ispassedV vialine to fractionation systemA '42 where it is separatedrinto a vrecycle stream lwithdrawn. via. line .43 and an overhead` leaving viaV line YM. lMost of the recycle is returnedvia line 15 tothe'second reactor 'fbut a sufficient volume is returned to the first Vreactor 3! Via line 48 to prevent an undue-build-up of the normal hexane. Therecyc-le may beitopped if desired. The overu head I"product leaving via -line 144; may4 be de butanized and used as such or may be subjected to further fractionation.

The following considerations apply to the invention in all of its aspects. The conversions may be the same in both reactors, but preferably the conditions are so adjusted that the per pass conversion is not above about 60 to 70% in the iirst reactor and not above about 30 to 40% in the second. The conversion increases with the temperature, the contact time and the boron iiuoride content of the catalyst, but decreases with increasing modiiier concentration. The exact conditions for optimum conversion are therefore somewhat interpendent but in general should be about as follows:

IPer cent by weight based on the weight of hydrogen' iiuoride employed.

Usually higher concentrations of the modier are maintained in the second reactor than in the` first. Themodiiler may be cycloparains or aromatics in concentrations of 2 to 25 weight percent-of the feed, or hydrogen at a partial pressure of 10 to 300 p.- s. i., or a combination of these; YRelatively `:high: concentrations of modifiers areY required in the second. reactor to preventv foririationl of lower and' high-boiling homologs from ,the .reactivey isohexanes. `.The optimum amount of modifier may be readily determined. by experiment. Cycloparans'will be largely isomerized in the` reactors 'andmay be recycled'if desired. Hydrogen may be recycled to the reactors withV the overhead from vthe azeotrope column.

lIt appears from experimental data that when normal hexane is lsomerized' (as in the rst reactor) in the..presenceof modifiers, the first product of the reaction is methyl pentanes providing the Vextent of conversion is not too great. Whenthe conversion Ais less thanl 'abouti 60=to 'Z0 theconcentratlcn of methyl pentanes may build up to to 50% of the ellluent from the catalyst chamber, with relatively small amounts of the hexanes going to other hydrocarbons. Usually the sum of neohexane and' diisopropyl does not exceed about 20% of the eiiluent, the ratio of vdiisopropyl to -neohexane being about 1.511. "With higher conversions of the normal hexane, the methyl pentanes are also converted but' the product is chieiiy hydrocarbons other than hexanes. V'The maximum'yield of methyl pentanes, diisopropyl and neohexanes is thus obtainedr in Ythe rst step at 'conversions of about or less.

f Similarly vit appears that Vmethyl pentanes-m'ay be isomerizedlas in the vsecond reactor) in the presence A4oi 'modiers' giving *high Ayields :of dlisopropyl providing' thel conversionisi-lotv above' about 35%. Y Y

Examples Iiechnicar'grade` rtl-hexane and 2-methyl pentaneA were charged in `separate runs kto a stirred reactor which was maintained at theA desired temperature and which was-about half full'l'of hydrofluoric' acid-boron fluoride catalyst. A small: amount of water and a reactor modifier were vpresent `inseach case. -fAfter'thet desired' reaction time the hydrocarbon phase was removed and analyzed. Data pertaining to the runs are cycling said last-named overhead to said second as follows: step, and passing said last-named bottoms to said .Run A B C D E F Charge n-Hexane n-Hexane n-Hexanc Z-Methyl Pentanc. Modier MCP 1. MCP1+H2 MC 2 Temperature, F.. 176 176.. 140 Time, Min Pressure, p. s. i 204 173 335 BF; in Catalyst, Wt. per cent 2. 1 3.1.. 4. 5

Feed Composition, Wt n-hexane 2lMethy1 pentane.

Methyl eyclopentane.

er cent Partial Pressure of Hydrogen, p. s. i.

Paran reacted, per cent 36 45. 0 56. 2 85. 3 33. 2 28.1

Cycloparafn reacted, Wt. per cent.. 45 (3) S2 81 92 Composition of Product, Wt. per cent: Y

' Pentanes and Lighter 0.5 2. 9 4. 4 1.1 1. 2 6.0

Neohexane 1. 1 3. 6 6.2 5. 3 5. 8 3. 1

Disopropyl 1. 9 6. 2 9. 2 17. 8 14. 7 16. 2

Methyl pentane 21. 9 27.8 33. 5 54. 6 62. 4 71. 9

Yn-Hexane 50. 6 52.3 41. 4 4. 9 15. 9

. Heptaues and heavier 2 24.0 7. 2 5. 3 1G. 3 2. 8

' l Methyl Cyclopcntane. 2 Includes cyclics.

l Not determined.

In a process with rst and second reactors the yield of the neoheXane-diisopropyl fraction is 82.2 Weight per cent ofthe n-hexane charged. The ASTM (clear) octane rating of this fraction should-be 85 to 99 or higher, depending upon the'eiciency of the fractionators. Throughout the specification, including the claims, it is intended that a reference to a small amount of Water present in the reaction zone shall mean an amount not exceeding the molecular equivalent of the boron fluoride present and that molecular equivalent" shall be understood to Y meanl mole for mole. In other words, the upper limit of water in either step of the isomerization process is one mole of Water for each mole of boron fluoride.

Iclaim:

1. A process for isomerizing normal hexane to diisopropyl and -neohexane which comprises isomerizing normal hexane in a i'irst step by means of a catalyst consisting essentially of hydrogen fluoride containing from 1 to 10 weight per cent of boron triiiuoride based on the hydrogen fluoride under relatively severe conditions to produce methyl pentanes as the vprincipal product, separating the eiiluent into an acid phase and a hydrocarbon phase, azeotropically 'distilling said hydrocarbon phase to produce an overheadof hydrogen fluoride," boron triflucride and some hydrocarbon and a bottoms of the heavier components, recycling said overhead to said rst step, fractionally distilling said bottoms in a fractional distillation zone to produce separate fractions of (1) pentanes and lighter, (2) neohexane and diisopropyl and (3) methyl pentanes, isomerizing said methyl pentanes in a second step by means of a catalyst consisting essentially of hydrogen fluoride containing from 1 to 10 Weight per cent of boron triuoride based on the hydrogen iuoride under relatively mild conditions to convert said methyl pentanes to diisopropyl and neohexane, separating the eflluent into an acid phase and a hydrocarbon phase, azeotropically distilling said hydrocarbon phase to produce an overhead of hydrogen fluoride, boron trifluoride and some hydrocarbon and a bottoms of the heavier components, re-

fractional distillation zone and distilling it there-v in together with said first-named bottoms.

2. A process for isomerizi-ng normal hexane ,to diisopropyl which comprises isomerizing normal hexane in a first step by vmeans of a catalyst consisting essentially of hydrogen fluoride con isomerizing said methyl pentanes so produced inV a second step by means of a catalyst consisting' essentially `of hydrogen fluoride containing from 1 to 5 weight per cent of boron triuoride based on the hydrogen uoride under relatively mild conditions compared to those employed in said' rst step and such'that the per pass conversionY of methyl pentanes is not above 40 per cent, the conversion temperature in said second stepheing from 100 to 200 F, and the contactarme being from 20 to 60 minutes and inthe presence of a larger amount than that employed in saidflrst step of a modifier which minimizes the formation of homologs to produce diisopropyl as the principal reaction product, and recovering the diisopropyl produced in said first and second steps as a product of the process.

3. A process for isomerizing normal hexane to diisopropyl which comprises isomerizing normal hexane in a rst step by means of a catalyst consisting essentially of hydrogen uoride containing from 1 to 1-0 weight per cent of boron triuoride based on the hydrogen fluoride under relatively severe reaction conditions such that the per pass conversion is not above per cent to produce methyl pentanes as the principal reaction product, in a, fractionation system separately recovering a'fraction of methyl pentanes and a fraction of diisopropyl from the resulting isomerization effluent, isomerizing said methyl pentanes in a secondstep by Vmeans of a catalyst consisting essentially of' hydrogenv fluoridev containing from l to 10 weight percent of boron 'fluoride based' on the hydrogen fluoride under reaction conditions which are relatively mild compared to those employed in said rst'step and such that the per pass conversion is not above 40 per cent to produce diisopropyl as the principal reaction product, and in said fractionation system recovering the unconverted methyl pentanes and the diisopropyl from the isomerization eiiluent from said second step together with said fraction of methylpentanes and said fraction of diisopropyl respectively.

4. A process forisomerizing normal hexane to diisopropyl which comprises isomerizing normal hexane in a rst step by means of a catalyst consisting essentially of hydrogen fluoride containing from 1 to 10 weight per cent of boron trifluoride based on the hydrogen fluoride under relatively severe reaction conditions such that izing saidv methyl pentanes in a second vvstepV by means of a catalyst consisting essentially of hydrogen 4fluoride containing from 1 to 10 weight per cent of boron trifluoride based on the hydrogen iiuoride under relatively mild conditions compared to those employed in said rst step and such that the per pass conversion of methyl pentanes is not above 40 per cent in the presence ofn a relatively large amount of a modier which minimizes the formation of homologs of isohexanes to produce diisopropyl as the principal reaction product, andin said fractionation system recovering the unconverted methyl pentanes and the diisopropyl from the isomerization effluent from said second step together with said fraction of methyl pentanes and said fraction of diisopropyl respectively.

5. The process of claim 2 wherein said modier in each of said first and second steps is methylcyclopentane in an amount lying between 2 and.25 per cent of the hydrocarbon feed.

`.6. A process for isomerizing normal hexane to diisopropyl and neohexane, diisopropyl being formed in major amount and neohexane being formed in minor amount, which comprises subjecting a feed consisting of 95 Weight per cent of normal hexane and 5 Weight per cent of methyl cyclopentane to isomerization in a first step by means of a catalyst consisting of hydrogen fluo- 8 ride .containing 2.1 Weight per centfof boron trifluoride, maintaining a temperature of' 17661V F. and a pressure of 204 pounds per square inch in said iirst step, holding the reactants in said rst step for 22 minutes and thereby eecting conversion of 45 per cent of said normal hexane with the production of methyl pentanes, diisopropyl and neohexane, the methyl pentanes being formed in major proportion and the diisopropyl and the neohexane being formed in minor pro! portion, segregating said methyl pentanes from the effluent of said iirst step and subjecting vsame to isomerization in a second step in the presence ,of 15.6 Weight per cent of methyl cyclopentane based on the hydrocarbon fed to the second step by meansof a catalyst consisting of hydrogen fluoride containing 2.1 Weight per cent oli-boronv triuoride, maintaining a temperature of 160 F. and a pressure of 112 pounds per square inchin said second step, holding the reactants inV said second step for 40 minutes and thereby effecting conversion of 35.3 per cent of the methyl pentane fed thereto, and thereby converting said methyl pentane fed to said second step to di-4 isopropyl in major proportion and 'neoheXane-in minor proportion, and recovering the diisopropyl and neohexane produced in said rst and second steps as a product of the process. y

7. The process of claim 3 in which a, small amount of Water not exceeding the, molecular equivalent ofthe boron iuoride is present in each of said rst and second steps. f

' HAROLD J. HEPP.

REFERENCES CITED The foiiowing references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,265,870 Schuit Dec. 9, 1941' 2,266,012 dOuvlle Dec. 16, 1941 2,278,934 Lee Apr. 7, 1942' 2,280,710 Lynch Apr. 21, 1942 2,283,852 Eglof May 19,' 1942 2,315,078 Pines Mar; 30, 1943 2,325,122 Ipatieff July 27, 1943 2,331,429 Sensel et al. Oct. l2, 1943 2,355,198 Atwell Aug. 18,1944' 2,357,495 Bloch Sept. 5, 1944 2,394,797 McAllister et al. Feb. 12, 1946 2,492,807 Egloi June 25, 1946 2,408,752 Burk Oct. 8, 1946 y FOREGN PATENTS Number 'Country Date Holland Mar. rz, 1942 Certificate of Correction Patent'No. 2,461,545. February 15, 1949.

HAROLD J. HEPP It is hereby certied that error appears in the printed specication of the above numbered patent requiring correction as follows:

Columns 5 and 6, in the table, fth column, line 11 thereof, for 85.3 read 35.3;

and that the said Letters Patent should be read With this correction therein that the same may conform to the record of the case in the Patent OfIice.

Signed and sealed this 23rd day of August, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oommtsst'oner of Patents. 

